DEVELOPING NEW CHEMICAL-RHEOLOGICAL MODELS AND … fileDi samping itu, indeks ketahanan kimia baru...

i

DEVELOPING NEW CHEMICAL-RHEOLOGICAL

MODELS AND CHEMICAL-DURABILITY INDICES OF

BITUMEN

MADI HERMADIHF-080011

A thesis submitted infulfilment of the requirement for the award of the

Doctor of Philosophy

Faculty of Civil and Environmental Engineering

Universiti Tun Hussein Onn Malaysia

NOVEMBER, 2013

v

ABSTRACT

Significant correlation among chemical properties, rheological characteristics and

durability of bitumen is very important in evaluating and modifying bitumen.

However, a number of previous studies found inconsistent correlation. Therefore, a

study on developing new chemical-rheological models and chemical-durability

indices was carried out. Two bitumen fractionation method, Rostler and Corbett

methods were used to extract each chemical fraction of bitumen. A number of

experiments were conducted to evaluate the effect of each chemical fraction on

bitumen rheology such as the effect of asphaltenes, polar aromatics, naphthene

aromatics, nitrogen bases, first acidaffins, second acidaffins and paraffins on elastic

modulus (G’), viscous modulus (G”) or fatigue factor (G*sin[δ]), and rutting fator

(G*/sin[δ]). Two bitumen from different sources, namely Petronas petroleum

bitumen and Buton rock asphalt (BRA) bitumen, were used. New chemical-

rheological models were formulated to estimate the bitumen rheology in corporating

parameters which are G’, G” or (G*sin[δ]), and (G*/sin[δ]) based on the chemical

properties. Furthermore, new chemical durability indices that may indicate the

ageing rate of bitumen during short-term and long-term ageing were also formulated.

Based on statistical analyses, the models and the indices, which were developed by

using chemical properties according to Rostler method were found to be invalid

because the real and the predicted rheology were significantly different. While

according to Corbett method the models and the indices were valid because the

differences is not significant since t-score of the models and the indices were

maximum 2.679 and 2.119 or less than t-critical 2.797 and 2.861 respectively). The

novelties of this study are the new models and the new indices can be used to predict

the bitumen rheology and ageing rate based on the chemical composition.

Furthermore, they are very important as guides in modifying a bitumen chemical

composition to produce a bitumen mixture with the desired rheology and short-term

or long-term ageing rate.

vi

ABSTRAK

Korelasi yang signifikan antara sifat kimia, ciri reologi dan ketahanan bitumen adalah

sangat penting dalam menilai dan mengubahsuai bitumen. Walau bagaimanapun,

beberapa kajian sebelum ini mendapati bahawa korelasi ini adalah tidak konsisten. Oleh

itu, satu kajian mengenai pembangunan model baru reologi-kimia dan indeks

ketahanan-kimia bitumen telah dijalankan. Dua kaedah pemeringkatan bitumen, iaitu

kaedah Rostler dan Corbett telah digunakan untuk mengekstrak setiap bahagian kimia

bitumen. Beberapa percubaan telah dijalankan untuk menilai kesan setiap bahagian

kimia terhadap reologi bitumen seperti kesan asphaltenes, polar aromatics, naphtene

aromatics, nitrogen bases, first acidaffins, second acidaffins dan paraffins kepada

modulus elastik (G’), modulus kelikatan (G"), factor ubah bentuk (G*sin[δ]) dan factor

aluran (G*/sin[δ]). Dua bitumen dari sumber yang berbeza, iaitu bitumen petroleum

Petronas dan asphalt batu Buton (BRA), telah digunakan. Model baru reologi-kimia

telah dirangka untuk menganggar ciri-ciri reologi bitumen, seperti G', G" atau G*sin[δ],

dan G*/sin[δ] berdasarkan sifat kimia. Di samping itu, indeks ketahanan kimia baru

yang menunjukkan kadar penuaan bitumen semasa jangka pendek dan jangka panjang

penuaan juga telah dirangka. Berdasarkan analisis statistik, model dan indeks yang

dibangunkan dengan menggunakan sifat-sifat kimia mengikut Rostler tidak sah kerana

reologi sebenar dan yang diramalkan berbeza secara ketara. Manakala menurut kaedah

Corbett, model dan indeks tersebut adalah sah kerana perbezaan sebenar dan yang

diramalkan tidak ketara atau t-skor model dan indeks adalah maksimum 2,679 dan

2,119 atau kurang dari pada masing-masing t-kritikal 2,797 dan 2,861. Penemuan ini

merangkumi model dan indeks baru yang boleh digunakan untuk meramalreologi dan

indeks ketahanan bitumen berdasarkan ciri-ciri kimia. Tambahan pula, penemuan ini

juga adalah sebagai panduan dalam mengubahsuai bitumen untuk menghasilkan

campuran dengan ciri-ciri reologi dan kadar penuaan jangka pendek atau jangka

panjang yang dikehendaki..

vii

TABLE OF CONTENTS

TITLE

DECLARATION

i

ii

DEDICATION iii

ACKNOWLEDGEMENTS iv

ABSTRACT v

ABSTRAK vi

TABLE OF CONTENTS vii

LIST OF TABLES xiii

LIST OF FIGURES

LIST OF SYMBOLS AND ABBREVIATIONS

xviii

xxiii

LIST OF APPENDICES xxvii

CHAPTER 1 INTRODUCTION 1

1.1 Background of study 1

1.2 Problem statement 6

1.3 Research aim and objectives 7

1.4 Research scopes 8

1.5 Thesis organization 9

CHAPTER 2 LITERATURE REVIEW 11

2.1 Introduction 11

2.2 Bitumen chemistry 13

2.2.1 Bitumen chemical properties according

to Rostler precipitation method 17


to Corbett chromatography method 19

viii


to other methods 21

2.3 Rheological characteristics of bitumen 26

2.3.1 Viscosity of bitumen 31

2.3.2 Rheological characteristics of bitumen to

address rutting and fatigue cracking 33

2.3.3 Rheological characteristics of bitumen to

address low temperature cracking 37

2.3.4 Short term ageing of bitumen 40

2.3.5 Long term ageing of bitumen 41

2.3.6 Performance grade bitumen specification 42

2.4 Relationship of Rostler bitumen component

fractions to bitumen durability 47

2.5

2.6

2.7

2.8

29

Relationship of Corbett bitumen component

fractions to bitumen durability

Asphalt mixture performance

2.6.1 Superpave mix design method of HMA

2.6.2 Mixture performance tests of HMA

Buton Rock Asphalt

2.7.1 History of Buton Rock Asphalt

2.7.2 Deposit of Buton Rock Asphalt

2.7.3 BRA Utilization as an asphalt

pavement binder

2.7.4 The utilization technology of Lawele

BRA as an asphalt pavement binder

Method in previous studies

Chapter summary

51

56

56

58

63

64

64

68

69

71

72

CHAPTER 3 RESEARCH METHODOLOGY 76

3.1 Introduction 76

3.2 Experimental approach

3.2.1 Extracting the chemical fraction

component of bitumen according to

76

ix

Rostler method (ASTM D 2006)

3.2.2 Extracting the chemical fraction

component of bitumen according to

Corbett method (ASTM D 4124)

3.2.3 Rheological characteristics tests of

bitumen by dynamic shear rheometer

3.2.4 Ageing conditioning of bitumen

3.2.5 Formulation of new chemical-

rheological models and chemical

durability indices of bitumen

3.2.6 Validation of chemical-rheological

models and chemical durability indices

77

78

80

80

81

82

3.3 Materials selection

3.3.1 Description of BRA bitumen

3.3.2 Description of petroleum bitumen

3.3.3 Description of aggregates

87

87

89

90

3.4 Selection of the experimental variables and

data analysis method 91

3.5

3.6

The differences of assessing technique

between previous and this study

Chapter summary

94

95

CHAPTER 4 EFFECT OF BITUMEN CHEMICAL

FRACTIONS BASED ON ROSTLER ON

RHEOLOGICAL CHARACTERISTICS OF

BITUMEN AND ITS CHEMICAL DURABILITY

INDICES 96

4.1 Introduction 96

4.2 Factorial analysis of the effect of chemical

fractions according to Rostler method on

bitumen rheological characteristics 97

4.3 Regression analysis of the effect of chemical

fractions according to Rostler method on

x


4.4 Effect of asphaltenes (based on Rostler) on


4.5 Effect of nitrogen bases on bitumen

rheological characteristics 106

4.6 Effect of first acidaffins on bitumen


4.7 Effect of second acidaffins on bitumen


4.8 Effect of paraffins on bitumen rheological

characteristics 110

4.9 Effect of test temperature on bitumen

rheological characteristics in the regression

equation (based on Rostler) 111

4.10 Effect of un-treatment constant on bitumen

rheological characteristics in the regression

equation (based on Rostler) 112

4.11 Proposed chemical-rheological models of

bitumen based on Rostler chemical properties 113

4.12

4.13

Proposed chemical durability indices of

bitumen based on Rostler chemical properties

Chapter summary

117

120

CHAPTER 5 EFFECT OF BITUMEN CHEMICAL

FRACTIONS BASED ON CORBETT ON

RHEOLOGICAL CHARACTERISTICS OF

BITUMEN AND ITS CHEMICAL DURABILITY

INDICES 122

5.1 Introduction 122

5.2 Factorial analysis of the effect of Corbett

chemical properties on bitumen rheological

characteristics 123

5.3 Regression analysis of the effect of Corbett

xi

chemical properties on bitumen rheological

characteristics 125

5.4 Effect of Corbett asphaltenes on rheological

characteristics of bitumen 129

5.5 Effect of polar aromatics on rheological


5.6 Effect of naphthene aromatics on rheological


5.7 Effect of saturates on rheological


5.8 Comparison of the effect of test temperature on

bitumen rheological characteristics based on

Rostler and Corbett 133

5.9 Comparison of the effect of non-treatment

constant on bitumen rheological characteristics

based on Rostler and Corbett 134

5.10 Proposed chemical-rheological models of

bitumen based on Corbett chemical properties 135

5.11

5.12

Proposed chemical durability indices of

bitumen based on Corbett chemical properties

Chapter summary

138

142

CHAPTER 6 VALIDATION OF THE NEW CHEMICAL-

RHEOLOGICAL MODELS AND CHEMICAL

DURABILITY INDICES OF BITUMEN 143


6.2 Chemical properties of the blended bitumen 144

6.3 Rheological characteristics of the blended

bitumen 146

6.4 Validation of the new chemical-rheological

models of bitumen

6.4.1 The new chemical-rheological models

based on Rostler chemical properties

155

155

xii

6.4.2 The new chemical-rheological models

based on Corbett chemical properties 160

6.5 Validation of the new chemical durability

indices of bitumen

6.5.1 The new chemical durability indices

based on Rostler chemical properties

6.5.2 The new chemical durability indices

based on Corbett chemical properties

165

166

167

6.6 Chapter summary 169

CHAPTER 7 PERFORMANCE OF BITUMEN AND ITS

MIXTURE 171


7.2 The optimum composition and volumetric of

the mixtures 172

7.3 Indirect tensile stiffness modulus 174

7.4 Dynamic creep stiffness 176

7.5 Fatigue test of long term aged mixture 178

7.6 Chapter summary 183

CHAPTER 8 CONCLUSION AND RECOMMENDATION 184

8.1 Conclusion 184

8.2 Recommendations 187

PUBLICATIONS DURING STUDY 189

REFERENCES 191

xiii

LIST OF TABLES

2.1 Structures and dipole moment values of some organic

molecules 16

2.2 Viscosity of bitumen fractions at same average

molecular weight (Petersen, 1982) 24

2.3 Performance Grade (PG) Specification of bitumen

(ASTM D6373 - 2007) 45

2.4 RDR value criteria for bitumen binder (Rostler, 1985) 48

2.5 Fractional composition of the original and aged Cold

Lake and Ural Bitumen in % (Michalica et al., 2008b) 53

2.6 Estimation of natural asphalt deposit in the world

(Deputy Minister of Energy and Mineral Resources,

1999) 65

2.7 Estimation of Lawele B.R.A. deposit (Ministry of Public

Work, 2006) 66

2.8 Requirement of Processed Lawele BRA (Directorate

General of Highway, 2009) 70

2.9 Requirement of Lawele BRA bitumen (Directorate

General of Highway, 2009) 70

3.1 Gradation limits for asphaltic concrete 83

3.2 Characteristics of BRA raw material 88

3.3 Characteristics of pre-processed BRA 89

3.4 Characteristics of BRA bitumen 89

3.5 Characteristics of the petroleum bitumen penetration

grade 80-100 (Petronas, Malaysia) 90

3.6 Characteristics of the fine and coarse aggregates 90

3.7 Factor and level of factor based on Rostler chemical

fractions 92

3.8 Factor and level of factor based on Corbett chemical

xiv

fractions 93

3.9 Variants 93

3.10 The differences of assessment technique between

previous and this study 94

4.1 Factor and level factor in the factorial strip plot design

analysis of the effect of Rostler chemical properties on

bitumen rheology 98

4.2 The factorial analysis results of the effect of the bitumen

chemical fraction based on Rostler method on complex

modulus (G*) 99

4.3 The factorial analysis results of the effect of the bitumen

chemical fraction based on Rostler on phase angle (δ) 99

4.4 Linearity analysis of the relationship between bitumen

chemical fractions based on Rostler with rheology

characteristics of non-aged bitumen 101



characteristics of RTFOT-aged bitumen 101



characteristics of PAV-aged bitumen 102

4.7 The coefficients in regression of the effect of bitumen

chemical fractions based on Rostler on rheological

characteristics of the non-aged bitumen 102



characteristics of the RTFOT-aged bitumen 103



characteristics of the PAV-aged bitumen 103

4.10 The average molecular weight number (Mn) of Cold

Lake bitumen and Ural bitumen using a vapour pressure

osmometer (VPO) (Michalica et al., 2008b) 105

xv

4.11 Carbonyl and sulfoxide index of the asphaltenes of Cold

Lake and Ural bitumen (Michalica et al., 2008b) 106

4.12 Elemental composition of the original and aged Cold

Lake and Ural bitumen (Michalica et al., 2008b) 111

4.13 The contribution of the Rostler chemical fractions of the

bitumen RTFOT Ageing Indices 118

4.14 The contribution of the Rostler chemical fractions of the

bitumen PAV Ageing Indexes

119

5.1 Factor and level factor in the factorial strip plot design

analysis of the effect of Corbett chemical properties on

bitumen rheology 123

5.2 The Analysis of variants results of the effect of the

Corbett chemical fractions on natural logarithmic of

complex modulus (ln G*) 124

5.3 The Analysis of variants results of the effect of the

Corbett chemical fraction on phase angle (δ) 124

5.4 Linearity of relationship between Corbett chemicals

with rheology of non-aged bitumen 126

5.5 Linearity of regression between Corbett chemicals with

rheology of RTFOT aged bitumen 126

5.6 Linearity of regression between Corbett chemicals with

rheology of PAV bitumen 127

5.7 The coefficients in regression of the effect of Corbett

chemicals on rheological characteristics of the non-aged

bitumen 127


chemicals on rheological characteristics the bitumen

after RTFOT 128


chemicals on rheological characteristics the bitumen

after PAV 128

5.10 The contribution of the Corbett chemical fractions on

Chemical Durability Indices of RTFOT-aged bitumen 140

xvi

5.11 The contribution of the Corbett chemical fractions of the

bitumen PAV Ageing Indices 140

6.1 Percentage of Rostler chemical fractions of the blended

bitumen 144

6.2 Percentage of Corbett chemical fractions of the blended

bitumen 145

6.3 Elastic modulus of the blended bitumen at non-aged

condition 146

6.4 Viscous modulus of the blended bitumen at non-aged

condition 147

6.5 Rutting factor of the blended bitumen at non-aged

condition 148

6.6 Elastic modulus of the blended bitumen at RTFOT-aged

condition 149

6.7 Viscous modulus of the blended bitumen at RTFOT-

aged condition 150

6.8 Rutting factor of the blended bitumen at RTFOT-aged

condition 151

6.9 Elastic modulus of the blended bitumen at PAV-aged

condition 153

6.10 Viscous modulus or fatigue factor of the blended

bitumen at PAV-aged condition

154

6.11 Comparison of rheological characteristics of the blended

bitumen at non-aged condition between actual and

predicted based on Rostler chemical properties 156


bitumen at RTFOT-aged condition between actual and



bitumen at PAV-aged condition between actual and


6.14 Rheological characteristics of the blended bitumen

based on actual tests and predicted using Rostler

xvii

chemical properties 159


bitumen at non-aged condition between actual and

predicted based on Corbett chemical properties 161


bitumen at RTFOT-aged condition between actual and



bitumen at PAV-aged condition between actual and


6.18 Rheological characteristics of the blended bitumen

based on actual tests and predicted using Corbett

chemical properties 164

6.19 Durability indices of the blended bitumen based on

actual tests and predicted by using Rostler chemical

properties

166

6.20 Durability indices of the blended bitumen based on

actual tests and predicted by using Corbett chemical

properties

168

7.1 The mixture volumetric at optimum compensations and

the requirement 174

7.2 Dynamic creep stiffness and bitumen rutting factor

estimated at 400C 177

7.3 Ageing and fatigue characteristics of bitumen and

mixture 179

xviii

LIST OF FIGURES

2.1 The broad structures of aliphatics hydrocarbon in

bitumen 13

2.2 The broad structures of cyclics hydrocarbon in bitumen 14

2.3 The broad structures of aromatics hydrocarbon in

bitumen 14

2.4 The combining structures of hydrocarbon in bitumen 14

2.5 Heteroatom structure of hydrocarbon in bitumen 15

2.6 Bitumen chemical precipitation test according to Rostler

method (ASTM D2006-1965) 18

2.7 Bitumen chemical sparation test according to Corbett

method (ASTM D4124-2001)

20

2.8 Glassy, elastic and viscous behaviour of bitumen (Breen

& Stephens, 1967)

27

2.9 Viscous, elastic and viscoelastic behaviour 28

2.10 Stress-strain response between the two extremes

bitumen (U.S. National Highway Institute, 2009) 29

2.11 Stress-strain response of viscoelastic bitumen (U.S.

National Highway Institute, 2009) 30

2.12 Viscous and elastic behaviour comparison of two typical

bitumen samples 30

2.13 Rheological characteristic tests at each ageing bitumen

condition (U.S. National Highway Institute, 2009) 31

2.14 Rotational Viscometer (U.S. National Highway

Institute, 2009) 32

2.15 Temperature – viscosity relationship (The Asphalt

Institute, 1996) 33

2.16 Oscillation at dynamic shear rheometer (U.S. National

xix

Highway Institute, 2009) 35

2.17 Used dimension in stress and strain calculations (U.S.

National Highway Institute, 2009) 35

2.18 Vertical and Horizontal Components of Complex

Modulus, (Hrdlicka, 2007) 36

2.19 Loading and Unloading of Asphalt Binder for the First

Three Cycles (Hrdlicka, 2007) 37

2.20 Schematic of bending beam rheometer (BBR) (National


2.21 The two evaluated parameters in BBR (U.S. National


2.22 DTT measurement principle (U.S. National Highway

Institute, 2009) 40

2.23 Typical changes in chemical composition of bitumen

(Brownridge, 2010) 50

2.24 The effect of ageing on chemical composition of binder

recovered from porous asphalt (Isacsso & Zeng, 1997) 54

2.25 Change composition of Ural and Cold lake bitumen

during ageing (Michalica et al., 2008) 54

2.26 SARA fractions for Ras Tanura and Riyadh bitumens

before and after 85 min and 340 min RTFOT ageing

(Lesueur, 2009)

55

2.27 SARA fractions for Kuwait and Bahrain bitumens

before and after 85 min and 340 min RTFOT ageing

(Lesueur, 2009)

55

2.28 Location and map of Buton Island (Ministry of Public

Work, 2006) 65

2.29 Kabungka BRA deposit of Sarana Karya 66

2.30 Lawele BRA deposit of Sarana Karya 67

2.31 Lawele BRA deposit of Buton Asphalt Indonesia 67

2.32 The effect of BRA percent on stiffness modulus of hot

mix asphalt mixture (Directorate General of Highway,

2006) 68

xx

3.1 Flow Chart of Research Activity 77

3.2 Chemical precipitation method according to Rostler 78

3.3 Chemical chromatography method according to Corbett 79

3.4 Chromatographic column for separation of bitumen by

elution-absorption 79

3.5 Correlation between loss on heating of BRA with

penetration of BRA-bitumen 88

4.1 The treatment-effect-coefficient of asphaltenes in the

regression equations based on Rostler composition 104

4.2 The treatment-effect-coefficient of nitrogen bases in the


4.3 The treatment-effect-coefficient of first acidaffins in the


4.4 The treatment-effect-coefficient of second acidaffins in

the regression equations based on Rostler composition 109

4.5 The treatment-effect-coefficient of paraffins in the


4.6 The treatment-effect-coefficient of temperatures in the


4.7 The non-treatment-effect-coefficient in the regression

equations based on Rostler composition 113

5.1 Comparison of the treatment effect coefficient between

Rostler and Corbett asphaltenes in the regression

equations 129

5.2 The treatment effect coefficient of polar aromatics in the

regression equations based on Corbett composition 130

5.3 The treatment effect coefficient of naphthene aromatics

in the regression equations based on Corbett

composition

131

5.4 The treatment-effect-coefficient of saturates in the

regression equations based on Corbett composition 132

5.5 Comparison of the treatment-effect-coefficient of

temperatures on the bitumen rheological characteristics

xxi

in the Rostler and Corbet regression equations 133

5.6 Comparison of the non-treatment effect coefficient in

the Rostler and Corbett regression equations 134

6.1 The effect of percentage of BRA bitumen on Rostler

chemical properties of the blended bitumen

144

6.2 The effect of percentage of BRA bitumen on Corbett

chemical properties of the blended bitumen

145

6.3 Elastic modulus of the blended bitumen at non-aged

condition 146

6.4 Viscous modulus of the blended bitumen at non-aged

condition 147

6.5 Rutting factor of the blended bitumen at non-aged

condition 148

6.6 Elastic modulus of the blended bitumen at RTFOT-aged

condition 149

6.7 Viscous modulus of the blended bitumen at RTFOT-

aged condition 150

6.8 Rutting factor of the blended bitumen at RTFOT-aged

condition 151

6.9 The effect of percentage of BRA bitumen ontemperature at which the Superpave requirement forG*/sin[δ] is fulfilled

152

6.10 Elastic modulus of the blended bitumen at PAV-aged

condition 153

6.11 Viscous modulus of the blended bitumen at PAV-aged

condition 154

6.12 Actual and predicted (based on Rostler chemical

composition) of the blended bitumen temperature at

G*/sin[] is fulfilled requirement 160

6.13 Actual and predicted (based on Corbett chemical

composition) of the blended bitumen temperature at

G*/sin[] is fulfilled requirement 165

7.1 The aggregate gradation of the mixtures 172

xxii

7.2 Mixing and compaction temperatures of petroleum and

BRA bitumen 173

7.3 Indirect tensile stiffness modulus of the mixtures with

different binders 175

7.4 Creep strain slope of the mixtures at 40 0C 177

7.5 Creep strain slope of the mixtures and G*/sin[] of the

bitumen at 40 0C 178

7.6 The correlation between G*sin[] of bitumen and

fatigue life of mixture at 400C 180

7.7 The correlation between percentage of BRA bitumen

and chemical durability indices of short-term age at

400C 180

7.8 The correlation between percentage of BRA bitumen

and chemical durability indices of long-term age at 400C 181

7.9 The effect of percentage of BRA bitumen on fatigue life

(Nf) at 400C of the asphalt mixture 181

7.10 The effect of the chemical durability index of short-term

ageing bitumen on fatigue life (Nf) of the asphalt

mixture at 400C 182

7.11 The effect of the chemical durability index of long-term

ageing bitumen on fatigue life (Nf) of the asphalt

mixture at 400C 182

xxiii

LIST OF SYMBOLS AND ABBREVIATIONS

A Asphaltenes

A1 First acidaffins

A2 Second acidaffins

AI Ageing Index

BBR Bending Beam Rheometer

BRA Buton Rock Asphalt, that natural rock asphalt from Buton

Island

CDI Chemical Durability Index

CDI-I Chemical Durability Index based on Rostler fractionation

method

CDI-II Chemical Durability Index based on Corbett fractionation

method

cP Centi Poises

CSS Creep Strain Slope

DSR Dynamic Shear Rheometer

DTT Direct Tension TestESALs Equivalent single axle loads

δ phase angle

FID Fame Ionization Detection

FTIR Fourier Transforms Infrared Spectroscopy

G’ Elastic modulus

G” Viscous modulus

G* Complex shear modulus

G*/sin[δ] Rutting factor to indicate rutting susceptibility

G*sin[δ] Fatigue factor to indicate fatigue susceptibility

Gmm Maximum specific gravity

GR Gotolski Ratio

xxiv

H2SO4 Sulfuric acid

85% H2SO4 Glover sulfuric acid

98% H2SO4 Concentrated sulfuric acid

H2SO4+SO3 Fuming sulfuric acid

H2S2O7 Fuming sulfuric acid

HP-GPC High Performance Gel Permeation Chromato-graphy

HMA Hot mix asphalt

HMAC Hot mix asphalt concrete

Hz Hertz

I.E.C. Ion Exchange Chromatography

IA Asphalten Index

IG Gastel Index

IC Colloidal Index

IDT Indirect tension

ITFT Indirect Tensile Fatigue Test

ITSM Indirect tensile stiffness modulus

Kabungka BRA Buton Rock Asphalt from Kabungka region

kPa Kilo Pascals

Lawele BRA Buton Rock Asphalt from Lawele region

Long-term ageing Ageing of bitumen during asphalt pavement construction

and in service

MP Melting point

N Nitrogen bases

Ni Gyration numbers at initial compaction

Nd Gyration numbers at design compaction

Nmax Gyration numbers at maximum compaction

OBC Optimum bitumen content

P Paraffins

Pa.S Pascal Second

PAV Pressure Ageing Vessel that used to simulate long-term

ageing condition of bitumen

PAV-aged After long-term ageing that simulated by PAV

PG Performance Grade

xxv

POBC Predicted optimum bitumen content

RDR Rostler Durability Ratio

RTFOT Rolling Thin Film Oven Test that used to simulate short-

term ageing condition of bitumen

RTFOT-aged After short-term ageing that simulated by RTFOT

RV Rotational Viscometer

SARA Saturates, Aromatics, Resin and Asphaltene

SGC Superpave Gyratory Compactor

Short-term ageing Ageing of bitumen during construction of asphalt

pavement

SHRP Strategic Highway Research Program

T Maximum applied torque,

TFOT Thin Film Oven Test that used to simulate short-term

ageing condition of bitumen

Tg Glass transition temperature

TLC Thin Layer Chromatography

TSR Tensile strength ratio

UTM Universal Testing Machine

UV Ultraviolet rays or electromagnetic radiation with a

wavelength shorter than that of visible light, but longer

than X-raysVMA Voids in Mineral Aggregate

Wc Work dissipated per load cycle,

shear stress

shear strain response

max Maximum applied shear stress

γmax Maximum response shear strain

σo Applied stress

0 Strain

R Radius of specimen

Deflection (rotation) angle

H Height of specimen

S(t) Creep stiffness at the time

xxvi

L Applied constant load or peak value of the applied vertical

load

B beam width

l Distance or length between beam supports

∆(t) Deflection at time

f Failure stress

Sm Indirect tensile stiffness modulus (MPa)

D Amplitude of the horizontal deformation

H Thickness of the test specimen

Poisson's ratio which for bituminous mixtures is normally

assumed to be 0.35

D(t) the creep compliance at time t (1/kPa),

GL Gage length (meters),

H Horizontal deformation (meters),

D Diameter of specimen (meters,),

Ccmpl nondimensional creep compiliance factor that is

calculated as 0.6354(X/Y)-1-0.332,

X/Y the ratio of horizontal to vertical deformation.

εx max Maximum tensile horizontal strain at the centre of the

specimen in micro-strain (µε)

σx max Maximum tensile stress at the centre of the specimen in

kPa,

Nf Fatigue life (number of cycles to failure)

0 Initial tensile (microstrain),

Stress (Newtons per square meter)

3600 strain at 3600th cycle

1200 strain at 1200th cycle

xxvii

LIST OF APPENDICES

APPENDIX TITLE PAGE

A The data of the effect of chemical properties basedon reactivity to sulfuric acid (Rostler method) onrheological characteristics of bitumen

201

B Regression analysis of the effect of chemical

properties based on reactivity to sulfuric acid

(Rostler method) on rheological characteristics of

bitumen

256

C The data of the effect of chemical properties based

on polarity (Corbett method) on rheological

characteristics of bitumen

266

D Regression analysis of the effect of chemical

properties based on polarity (Corbett method) on

rheological characteristics of bitumen

292

E Rostler chemical composition, predicted and actual

rheological characteristics of the blended bitumen

302

F Corbett chemical composition, predicted and actual

rheological characteristics of the blended bitumen

318

G Statistical analysis of validation of chemicals-

rheological models and chemical-durability indices

based on Rostler and Corbett methods

334

1

CHAPTER 1

INTRODUCTION

1.1 Background of study

The worldwide need of petroleum bitumen is continuously increasing but the supply

is limited and the price tends to increase continuously. On the other hand, there is a

potential deposit of natural rock asphalt in Buton Island, Indonesia. It is called

Buton Rock Asphalt (BRA) that consists of around 30% bitumen (Affandi, 2012).

Currently, BRA is not fully utilized because the bitumen should first be modified to

ensure that its characteristics could meet the current bitumen specification. A proper

modification method requires knowledge about the chemical composition and its

relation with the rheological characteristics of bitumen.

A significant relationship among chemicals, rheology and durability of

bitumen can be used as guidance in modifying bitumen, including BRA bitumen;

however, previous studies have indicated that they were not significantly related (Lu,

2002; Hermadi & Sjahdanulirwan, 2005; Michalica, Daucik & Zanzotto, 2008b)

thus, there is a need to study and find a new approach, as claimed in this study.

1.1.1 The needs and sources of bitumen

Bituminous mixture or asphalt is a commonly used pavement material around the

world. It plays a vital role in global transportation infrastructure, drives economic

growth and social well-being in developed as well as developing countries

(Mangum, 2006). In addition to the construction and maintenance of roads and

2

highways, bitumen is also used extensively for airport runways and taxiways, private

roads, parking areas, bridge decks, footways, cycle paths, and sports and play areas.

Asphalt covered more than 90 % of the four million kilometres of roads and

highways and about 85% of airport runways in North America. A similar percentage

of 5.2 million kilometres of roads and highways in Europe are also covered with

asphalt whilst in Asia, about four million kilometres of roads are surfaced with

asphalt (EAPA and NAPA, 2011).

About 1,600 million metric tonnes of asphalt were produced during the year

of 2007 alone (EAPA & NAPA, 2011). With bitumen content within the range of

five to six % of total weight of asphalt mix and bitumen for other applications such

as chip seal, prime and tack coats, it is estimated that the current world use of

bitumen is approximately 102 million metrical tonnes per annum. The vast majority

of bitumen (85%) is used in asphalt pavement. Around 10% are used in roofing

application and the remainder for a variety of other purposes (The Asphalt Institute

& Eurobitum, 2011). Global consumption of bitumen is forecasted to advance 4.1 %

annually from a very weak 2010 base to 119.5 million metric tons in 2015, which is

equivalent to 725 million barrels of primary bitumen (The Freedonia Group, 2012).

The main source of bitumen that the world relies on is petroleum where the

availability and price of bitumen are depending on the reserve, production and price

of crude oil. It is well recognised that, for crude oil supply, the world depended very

much on the Middle East and the North African region. Proven crude oil reserve of

this region is about 727.5 billion barrel which accounted for almost 70 % of the

global oil reserve and contributed about 30% of the world crude oil production

(Okogu, 2003). However, instability of geopolitical conditions in the Middle East

constantly provokes the crude oil price escalation and world anxiety of supply

shortage of petroleum.

In the last decade, the increase of crude oil price has significantly increased

the price of bitumen. The bitumen price increment as high as 250% during the

period of 2005 to 2008 were reported (Portland Cement Association, 2009). It is

estimated that the bitumen supplies will likely become more expensive and

unreliable in future.

Besides the political situation in the middle-east and economic distress in

many countries, there are two other reasons for the price increment. Firstly, as non-

3

renewable material, crude oil prices increased continuously and as a result, the

bitumen prices also increased. Secondly, the changes in oil refining practices have

led to a reduction in heavy crude production. This production shift was made

possible by supplementing existing refining processes with equipment called cokers.

Refineries with installed cokers produce fewer lower-margin residual products such

as bitumen (Portland Cement Association, 2009). Therefore, it is realistic to look for

other alternatives of refined bitumen such as Portland cement, recycling asphalt

mixture, and exploring natural bitumen reserve. Natural bitumen is reported in 586

deposits in 22 countries. It occurs in clastic and carbonate reservoir rocks and

commonly in small deposits at, or near, the earth’s surface. One of them is Buton

Island deposit in Indonesia (Attanasi & Meyer, 2007). The current production levels

of natural extra-heavy oil and natural bitumen in the world is just under 2% of world

crude oil production (Attanasi & Meyer, 2007).

1.1.2 Potential of Buton Rock Asphalt

The use of Buton Rock Asphalt (BRA) as an alternative to petroleum bitumen has

been explored with total estimated deposit of above 700 million tons (Ministry of

Public Work, 2006). It is probably the largest source of rock asphalt in the world.

However, the utilization of BRA in the past was limited mainly because, as a

naturally occurring material, BRA has a number of disadvantages compared to

conventional bitumen such as:

(i) Bitumen of BRA is impregnated inside the rock;

(ii) Bitumen content of BRA is low and widely varies (in range 10% to 30%);

(iii) Wide variation of bitumen consistency (i.e. from very hard to very soft);

(iv) High water content,

The disadvantages of BRA are expected to cause difficulties during the

construction process as well as low quality of the final product (asphalt mixes). The

low bitumen content makes the transportation cost of BRA high because only a small

proportion of the transported material is bitumen while the rest is rock which, in case

of conventional bitumen, should be available locally at project sites.

In order to overcome the above problems, ideally, bitumen of BRA should be

4

extracted to produce bitumen identical to conventional petroleum bitumen.

According to Affandi (2012), especially for BRA from Lawele region, pure BRA

bitumen can be categorized as PG 70 or better than petroleum bitumen penetration

grade 60/70 that is mostly categorized as PG 58.

Refinery of rock asphalt would be expensive because unlike refinery of crude

oil; it required a large quantity of additional solvent, which may not be 100%

recoverable, and it only produces a single end product which is bitumen. In the past,

this option would not be economically competitive enough; however, as the source

of petroleum bitumen has declined and the price of crude oil increased, it is believed

that the refinery of BRA is becoming profitably feasible thus; the extracted bitumen

can be utilized as ordinary bitumen.

1.1.3 The importance of chemical properties of bitumen

As a binder, bitumen should have the physical properties desired to produce stable

asphalt in terms of its ability to carry the traffic and its durability or ability to

maintain its performance during the expected service life. The performance of

bitumen includes all phases of its life from spraying, mixing, laying, compaction,

and its service life. In the latter, resistance to plastic deformation and fatigue

cracking is especially important.

As thermoplastic and viscoelastic material, bitumen characteristic is affected

by temperature, loading and duration of loading, its behaviour under applied force or

stress can better describeits rheological properties.

Superpave uses dynamic shear rheometer (DSR) to characterize the elastic

(G’) and viscous (G”) behaviour of bitumen (ASTM D7175) at the high and

intermediate pavement service temperature. The DSR measures the complex shear

modulus (G*) and phase angle (δ). Superpave uses G*/sin[δ] to address rutting

susceptibility, and G*sin[δ] to indicate fatigue cracking resistance.

It is widely known that characteristic and performance of bitumen are

strongly affected by its chemical properties. Theoretically, it should be possible to

correlate the change of bitumen behaviour under different temperature and duration

5

of loading with its chemical composition. The knowledge on this matter can be

utilized to evaluate and modify or improve conventional bitumen.

However, bitumen consists of thousands of different hydrocarbon molecules

with different and complex chemical structure. As a result, the effect of chemical

properties on performance of bitumen is complicated and difficult to identify.

Moreover, publications related to this subject were also quite limited.

Lu &Isakson (2002) found that chemical and rheological changes were

generally inconsistent. Michalica et. al. (2008a) concluded that there is definite

relationship between the chemical and rheological (physical) properties of bitumen

however it is very complex due to the concurrent actions of various material

properties. Chiu & Chiu (2008) stated that the composition test based in fractional

separation is not consistent with field performance.

Most of the research used advanced instrumentation to analyse and determine

the chemical composition of bitumen. The work involved a number of bitumen from

different sources with different chemical composition. Rheology of each bitumen

was then determined, and the correlation between thechemical composition and

rheology of bitumen was developed. It is postulated that the inclusiveness of the

reported results appeared because of the effect of each fraction cannot be

distinguished or identified. To address this problem, a new technique to identify the

contribution of each chemical fraction on rheology is necessary.

The current practice to identify durability of bitumen is either by (i)

comparing the amount of the more reactive to the less reactive to the environment

with hydrocarbon molecules of the bitumen, or (ii) comparing the physical or

rheology of bitumen before and after short-term and long-term ageing (Demirebs,

2002; Kumar et al., 2009; Michalica et al., 2008b,). The earlier is known as the

durability ratios while the latter is the ageing indices.

Two durability ratios have been introduced in the past. They are Rostler

Durability Ratios (RDR) and Gotolski Ratios (GR). Both are based on the ratio of

the reaction amount of hydrocarbon molecules to sulphuric acid. Both ratios can be

illustrated as Equation (1.1) and Equation (1.2).

(1.1)

5































(1.1)

5































(1.1)

6

(1.2)

where:

Nb = nitrogen bases

A1 = first acidaffins

A2 = second acidaffins

P = paraffins

A = asphaltenes

It can be seen from the above formulations that Rostler and Gotolski have

different opinion regarding the reactivity of the second acidaffins and asphaltenes.

These two formulas had been subjected to a number of critics and being rejected by

scientists and practitioners thus both indices were never being used in any bitumen

specification.

Expression of the durability of bitumen by comparing the physical or

rheology of bitumen before and after ageing has been adopted worldwide. For

examples, penetration before and after Thin Film Oven Test(TFOT) was adopted in

ASTM D946 Standard Specification for Penetration-Graded Asphalt Cement for

Use in Pavement Construction. Viscosity before and after TFOT was adopted in

ASTM D3381 Standard Specification for Viscosity-Graded Asphalt Cement for Use

in Pavement Construction. Rheology before and after short-term ageing by Rolling

Thin Film Oven Test (RTFOT) and long-term ageing by Pressure Ageing Vessel

(PAV) aged was adopted by Strategic Highway Research Program (SHRP)

specification, which later also adopted by ASTM D 6373 Standard Specification for

Performance Graded Asphalt Binder. Nevertheless, the usefulness of these indices

are limited because they do not provide any information on why and how the ageing

of bitumen different from each other.

1.2 Problem statement

From the preceding discussion, it may be concluded that the need for petroleum

bitumen worldwide is increasing but the supply is limited and the price tends to

6

(1.2)

where:

Nb = nitrogen bases



P = paraffins

A = asphaltenes





specification.

















6

(1.2)

where:

Nb = nitrogen bases



P = paraffins

A = asphaltenes





specification.

















7

increase continuously due to political instability of the Middle East and world

anxiety of petroleum supply shortage. In another hand, there is a large deposit of

BRA in Buton Island that is a potential to substitute petroleum bitumen but currently

has not been fully explored. Some BRA consists of bitumen that does not meet the

requirement of asphalt binder. Improvement of the quality of bitumen (either

petroleum or natural bitumen) can be implemented effectively if a solid knowledge

on chemical-rheological relationship of bitumen was available however; previous

study found that the correlation is not significant (Lu, 2002; Hermadi &

Sjahdanulirwan, 2005; Michalica, Daucik & Zanzotto, 2008b) hence, in order to

develop the knowledge of the correlation between chemical properties and

rheological characteristics of bitumen to use in improving the performance of

bitumen, some problems were identified and stated as follows:

(i) Chemical properties of bitumen and how they affect the performance of

bitumen, in terms of rheology and durability is not fully understood.

(ii) Although it is acknowledged that a strong relationship between the chemical

properties and performance of bitumen exist, most researchers tried to

develop a structured relationship which leads to inconclusive results.

(iii) Guidance on how to utilize the knowledge of chemical-rheological bitumen

to improve the performance of bitumen is presently not available.

1.3 Research aim and objectives

The above stated problem provided a justification for the aim of the experiment

described in this thesis, which directed toward the development of new chemical-

rheological models and chemical durability indices of bitumen. A different approach

in assessing the effect of chemical fractions on the rheology of bitumen is required.

The approach should be simple yet able to distinguish the effect of individual

chemical fractions.

From the arguments presented above, the specific objectives of the study are

as follows:

8

(i) To develop a new technique for the assessment on the effect of chemical

fractions on rheology and durability of bitumen.

(ii) To develop new models of chemical-rheological characteristics and chemical

durability indices of bitumen.

(iii) To verify the models and indices by experimentally studying the relationship

between chemical and rheological characteristics of bitumen of different

sources.

1.4 Research scopes

The scopes of this research are as follows:

(i) The two sources of bitumen were used in this study that is the BRA bitumen

from Lawele region in Indonesia and petroleum bitumen penetration grade

80-100 dmm from Kemaman Malaysia.

(ii) The coarse and fine aggregates used in this experiment were from Hanson

quarry in Batu Pahat, Malaysia.

(iii) In reviewing the physical characteristics of the bitumen, the specifications

used were penetration grade specification (ASTM D 946) and performance

grade specification (ASTM D 6373).

(iv) Ageing bitumen was conducted artificially in the laboratory. The standard

test methods used were RTFOT (ASTM D2872) for short-term ageing and

PAV (ASTM D 6521) for long-term ageing.

(v) In this study, two standard test methods to evaluate the chemical properties of

the bitumen were used. These were ASTM D 2006 “Method of Test for

Characteristic groups in Rubber Extender and Processing Oils by the

Precipitation Method” and ASTM D 4124 “Standard Test Methods for

Separation of Asphalt into Four Fractions”. ASTM D 2006 separated the

9

bitumen into five fractions based on their reactivity to sulphuric acid and

ASTM D 4124 separated the bitumen into four fractions based on their

polarity. The other test methods, such as Thin Layer Chromatography (TLC),

Size Exclusion High Performance Gel Permeation Chromatography (HP-

GPC), Ion Exchange Chromatography (IEC), and Fourier transforms infrared

spectroscopy (FTIR) were not used because those methods cannot physically

isolate and extract the chemical fractions of bitumen. The extracted fractions

were very important in the experiment to evaluate each fraction’s effect on

the bitumen rheological characteristics.

(vi) The test method that was used to evaluate the bitumen rheological

characteristic was ASTM D 7175 Determining the Rheological Properties of

Asphalt Binder Using a Dynamic Shear Rheometer. By this method, the

viscous modulus, the elastic modulus, deformation susceptibility at high

temperature and crack susceptibility at medium range temperatures (which

addressed fatigue cracking) could be evaluated. The other test methods, such

as Bending Beam Rheometer (BBR) and Direct Tension Test (DTT) which

addressed cracking at a low temperature were not covered in this study.

(vii) Mixture performance test on the bituminous mixture of BRA and petroleum

bitumen were based on Superpave guide line. The tests covered testing and

evaluated the mechanistic properties of bituminous mixtures using Universal

Test Machine to test Creep stiffness, Indirect Tensile Stiffness Modulus, and

Indirect Tensile Fatigue.

1.5 Thesis organization

This thesis is organized into eight chapters. The background and purposes of the

research program are presented in this first chapter. The scope of the research

program along with the objectives is discussed.

Chapter Two provides a review on chemical and rheological of bitumen,

asphalt mixture performance and Buton Rock Asphalt including chemical and

rheological of bitumen, characterizations and correlation of both. Asphalt mixture

10

performance was discussed covering Superpave volumetric mix design, permanent

deformation, fatigue cracking, low temperature cracking, moisture damage, and

ravelling effort. Furthermore, Chapter Two also describes location, deposit and

current utilization technology of BRA as asphalt binder.

Methodology of this study is described in Chapter Three which includes

experimental design, preparation of samples, chemical properties tests, rheological

characteristics tests, and ageing conditioning of bitumen. Performance tests of

asphalt mixture and data analysis are also covered within this chapter.

Chapter Four and Five present the results and discussion on the effect of

chemical properties on rheological characteristics of bitumen. Chapter Four based

on Rostler chemical properties, while Chapter Five based on Corbett's chemical

properties. Development of new chemical-rheological models and chemical

durability indices are discussed in both chapters. Furthermore, validation of the

models and the durability indices are described in Chapter Six and Seven. The

validation based on bitumen rheological characteristics is in Chapter Six and based

on mixture performance is in Chapter Seven.

Finally, the conclusion and recommendation that made through the study are

presented in Chapter Eight.

11

CHAPTER 2

LITERATURE REVIEW

2.1 Introduction

This chapter elaborates the chemical properties and rheological characteristics of

bitumen, their methods of measurement, relationship with asphalt mixture

performance, and Superpave performance grade (PG) specification of bitumen that

was developed through the Strategic Highway Research Programme (SHRP).

Furthermore, this chapter also discusses about Buton Rock Asphalt (BRA), covering

its history, potential deposit, and current utilization technology as a binder of asphalt

pavement.

Theoretically, bitumen characteristics are formed by each chemical

component characteristic. Therefore, the chemical composition of bitumen is useful

for evaluating and modifying a bitumen composition to produce bitumen with better

physical and rheological characteristics however; bitumen consists of thousand types

of hydrocarbon molecules, which make it practically impossible to analyse the

bitumen based on its individual molecule type thus the chemical composition of

bitumen is usually analysed by chemical fractionation.

In fractionation, the molecules which have the same characteristics were

grouped in one fraction. According to Rostler method (ASTM D2006), bitumen is

fractionated to five fractions according to their reactivity to sulphuric acid. The

fractions are asphaltenes, nitrogen bases, first acidaffins, second acidaffins, and

paraffins. Corbett (1969) suggested a method to analyse bitumen chemical

composition based on their polarity. The fractions are asphaltenes, polar aromatics,

naphthene aromatics, and saturates. This method was standardized as ASTM D4126.

12

The other methods of fractionation are based on similarity of molecule

weight, acidity-alkalinity and functional groups. These methods are also discussed

throughout this chapter.

Rheological characteristic of bitumen is important because it influences the

performance of asphalt mixtures from the construction stage up to the in-service

lifetime.

Bitumen is a viscoelastic material which exhibits both viscous and elastic

characteristics when undergoing deformation (Kamboozia & Arabani, 2012; Meyer

& Chawla, 2009). The rheological characteristics depend on temperature and the

level of ageing. At high temperatures, such as during mixing and compaction of

asphalt, bitumen dominantly exhibits viscous behaviour, while at very low-in-service

temperature bitumen exhibits more as elastic material. In between these two

extremes, it exhibits as viscoelastic material.

Bitumen of hot mix asphalt is subjected to non-ageing or fresh, short-term

ageing, and long-term ageing conditions. These conditions are related with before

construction, after construction or early in-service and after long-term in-service

condition stages of asphalt respectively. Performance of asphalt in terms of its

resistance to permanent deformation and fatigue can be explained based on the

rheological characteristics of its bitumen at relevant age condition.

Understanding the relationship of chemical properties with rheological

characteristic of the bitumen is very useful in investigating and modifying the

bitumen. Most chemical separation is based on the reactivity or polarity of the

various molecular types thus bitumen molecules can be conveniently separated or

grouped into molecular types or fractions with a narrower range of properties based

on their chemical functionality. The separation and classification of molecular types

have been useful in providing chemically definitive component fractions for further

characterization, thus aiding in determining how different molecular types affect the

physical or rheological and chemical properties of the whole bitumen and how the

bitumen mixer differs chemically from one another (Petersen, 2009).

13

2.2 Bitumen chemistry

Bitumen is a complex mixture of organic molecules which varies widely in its

composition, molecular weight, and compound types with hydrocarbon as dominant

molecules (Petersen, 2009). It also consists of heterocyclic and functional groups

containing oxygen, sulphur and nitrogen, even in a minor amount. Metals, such as

iron, nickel, magnesium calcium, vanadium, etc., may also be found in bitumen in

traced quantities (Airey, 1997; Meyer & Witt, 1990). All chemical molecules have a

contribution on bitumen characteristics such as chemical, physical, rheological and

ageing. However, the composition of bitumen is very complex. The number of

molecules with different chemical structure is extremely large hence it is impossible

to separate and identify every different molecule. Currently, the chemical

composition of bitumen is characterized by separating different groups or fractions

based on chemical reactivity, precipitation or solubility, chromatography, molecular

size and spectroscopic (Bell, 1989; Youtcheff & Jones, 1994).

There are three broad group structures of hydrocarbon molecules in bitumen,

namely aliphatic, cyclics and aromatics (Robertson, 1991; Berkers, 2005; Polacco et

al., 2008; Jones, 1992; Lesueur, 2009). The structures are shown in Figures 2.1, 2.2

and 2.3. The other molecules are a combination of them as shown in Figure 2.4.

While the major mass of bitumen is hydrocarbons, large proportion of molecules

also contained one or more heteroatoms such as nitrogen, sulphur, oxygen and

metals as shown in Figure 2.5. As a single structure, the molecules are non-polar but

if the structure is combined with each other or contained heteroatoms, the molecules

became polar. The polarity of molecules that indicated by Dipole moment value at

various molecule structures are shown in Table 2.1.

Saturate un-saturate

Figure 2.1: The broad structures of aliphatic hydrocarbon in bitumen

13



























13



























14

Figure 2.2: The broad structures of cyclics hydrocarbon in bitumen

Figure 2.3: The broad structures of aromatics hydrocarbon in bitumen

Figure 2.4: The combining structures of hydrocarbon in bitumen

14




14




15

Sulfoxide Ketone

Carboxylic Amine

Organo-metalic of vanadium

Figure 2.5: Heteroatom structures of hydrocarbon in bitumen

15

Sulfoxide Ketone

Carboxylic Amine



15

Sulfoxide Ketone

Carboxylic Amine



16

Table 2.1: Structures and dipole moment values of some organic molecules

Names Structures Dipole Moment Polarity

Hexane 0.00 D

Cyclohexane 0.00 D

Less-Polar

Benzene 0.00 D

Toluene 0.36 D

0-xylene 0.45 D

Chlorobenzen 1.57 D

Water H2O 1.87 D

Pyridine 2.37 D

More Polar

16



Hexane 0.00 D

Cyclohexane 0.00 D

Less-Polar

Benzene 0.00 D

Toluene 0.36 D

0-xylene 0.45 D

Chlorobenzen 1.57 D

Water H2O 1.87 D

Pyridine 2.37 D

More Polar

16



Hexane 0.00 D

Cyclohexane 0.00 D

Less-Polar

Benzene 0.00 D

Toluene 0.36 D

0-xylene 0.45 D

Chlorobenzen 1.57 D

Water H2O 1.87 D

Pyridine 2.37 D

More Polar

17

2.2.1 Bitumen chemical properties according to Rostler precipitation method

The test method based on solubility and chemical reactivity was developed by

Rostler-Stenberg and had been standardized in ASTM D2006-1965 Method of Test

for Characteristic Groups in Rubber Extender and Processing Oils by the

Precipitation Method which was discontinued in 1976. Nevertheless, the standard is

still being used in evaluating, modifying or rejuvenating bitumen. Boyer (2000),

Siswosoebrotho et al., (2005), Houston et al., (2005), Shen et al., (2007), and

Brownridge, (2010) used the test standard in evaluating bitumen.

Basically, the test separates bitumen into five fractions, namely asphaltenes

(A), nitrogen bases (N), first acidaffins (A1), second acidaffins (A2) and paraffins

(P). The percentage of asphaltenes is the amount of bitumen that is insoluble in low

molecular weight of normal paraffins such as n-pentane, n-hexane and n-heptane.

Nitrogen base percentage is the amount of bitumen parts that is soluble in low

molecular weight of normal paraffins but become insoluble after being treated by

glover sulphuric acid (85% sulphuric acid, H2SO4). The percentage of the first

acidaffins is determined by calculating the amount of the bitumen fractions that is

soluble in low molecular weight of normal paraffins and still soluble after being

treated with glover sulphuric acid, however, the fraction becomes insoluble after

being treated by concentrated sulphuric acid (98% sulphuric acid). The percentage

of second acidaffins is the amount of the bitumen fractions that is soluble in low

molecular weight of normal paraffins and still soluble after being treated with glover

and concentrated sulphuric acid. The second acidaffins becomes insoluble after

being treated by fuming sulphuric acid (H2SO4+30%SO3 or H2S2O7). The last

fraction is paraffins percentage of bitumen fractions that is soluble in low molecular

weight of normal paraffins and after being treated by glover, concentrated and

fuming sulphuric acids. The test method is showed in Figure 2.6.

Asphaltenes are large, discrete solid inclusions of bitumen. They are

responsible for the presence of structure in asphalts and for their non-Newtonian

rheological behaviour. They are the most highly polar molecules, insoluble in non-

polar solvent such as low molecular weight normal paraffins. The function of

asphaltenes in bitumen is as the thickening, structuring or bodying agent and impart

strength, stiffness and colloidal structure (Boyer, 2000; Oyekunle, 2005).

18

Asphaltenes are most complex molecules presented in bitumen containing aliphatic

hydrocarbon side chines, aromatics core system, heteroatoms and metals (Siddiqui,

2003). Oyekunle (2006) described asphaltenes as a black or brown coloured, hard,

non-plastic, non-malleable high molecular weight compound ranging between 1,200

and 200,000 g/mol. They contain predominantly carbon and hydrogen with sulphur,

oxygen, nitrogen and other heteroatoms. Hardee (2005) found asphaltenes as a

brittle amorphous solid, which are highly condensed aromatic compounds with

molecular weight 2,000-5,000 g/mol and constitute to 5-25% of the total weight of

asphalts.

Figure 2.6: Bitumen chemical precipitation test according to Rostler method (ASTMD2006-1965)

Deasphaltene bitumen or parts of bitumen which is soluble in low molecular

weight of normal paraffins, such as n-pentane, n-hexane and n-heptane are called

petrolenes or maltenes (Lesueur, 2009). According to Rostler method (ASTM D

2006), maltenes is defined as parts of bitumen, which is soluble in n-pentane. It

consists of nitrogen bases, first acidaffins, second acidaffins and paraffins.

Nitrogen bases are polar compounds. It is a bitumen fraction of highly

reactive resins, which acts as a peptizer for the asphaltenes (Boyer, 2000; Petersen,

2009). Nitrogen bases mostly consist of hydrocarbon containing nitrogen molecules,

19

however, it also contains all molecule bases and heteroatoms that can react and

precipitated with glover sulphuric acid.

First acidaffins are resinous hydrocarbon components, which functions as a

solvent for the peptized asphaltenes (Boyer, 2000). The molecules are mostly

consisted of aromatics.

Second acidaffins are components of slightly unsaturated hydrocarbon that

also serve as a solvent for the peptized asphaltenes (Boyer, 2000).

Paraffins are saturated hydrocarbon, functioning as bonding agent for the

asphalt components (Boyer, 2000). The molecules consist of saturated, aliphatic and

cyclic which cannot react with fuming sulphuric acid.

2.2.2 Bitumen chemical properties according to Corbett chromatography

method

The test method was introduced by Corbett & Swarbrick (1969) based on

absorption-desorption chromatography and has been standardized in ASTM D 4124-

2001 Standard Test Methods for Separation of Asphalt into Four Fractions. As

shown in Figure 2.7, the test separates the bitumen based on solubility and polarity

grade into four components which are asphaltenes, saturates, naphthene aromatics,

and polar aromatics. Asphaltenes is the insoluble part of bitumen in n-heptane

solvent. Saturates or saturated oil components is the soluble part of bitumen in n-

heptane solvent and cannot be absorbed by alumina absorbent. Naphthen aromatics

or aromatics oil component is the soluble part of bitumen that can be absorbed by

alumina absorbent and can be eluted by toluene solvent. Polar aromatics or resin

component is the soluble part of bitumen that can be absorbed by alumina absorbent

and can be eluted by trichloroethylene solvent or mix of methanol and toluene in 1:1

proportion.

Asphaltenes based on Corbett method and Rostler test is basically identical as

an insoluble part of bitumen in low molecular weight normal paraffins.

Saturates fraction of bitumen is a mixture of pure aliphatics, aliphatics with

side chains, cycloaliphatics, and cycloaliphatics with side chains. The average

molecular weight of the oil is in the C40-C50 range, and it is colourless liquid. The

20

average molecular weight is around 600 g/mol with very few polar atoms or

aromatic ring content (Lesueur, 2009). Saturates are viscous liquids or solids

ranging from straw to clear in colour, consisting mainly of a long chain saturated

hydrocarbons with some branched chain compounds, alkyl aromatics with long side

chains and cyclic paraffins (naphthenes), with molecular weights of 500-1,000

g/mol. It constitutes 5-20% of the total weight of the asphalt (Hardee, 2005).

Figure 2.7: Bitumen chemical separation test according to Corbett method (ASTM D4124-2001)

Naphthene aromatics or aromatics are the most abundant constituents of

bitumen binder together with polar aromatics or resins, since they contain about 30 -

45% of the total bitumen. They consist of several aryl groups connected by aliphatic

chains and appear as yellowish to red liquid at room temperature. They are

somewhat more viscous than saturates at the same temperature because of a higher

glass transition temperature around -20oC. The average number of molecular weight

is around 800 g/mol (Lesueur, 2009). According to Hardee (2004), naphthen

aromatics are viscous dark-brown liquids containing mainly carbon, hydrogen and

sulphur with minor amount of oxygen and nitrogen, with a molecular weight of 500-

900 g/mol, which constitutes to 45-60% of the total weight of bitumen.

Polar aromatics that are also called resins consist of aliphatics, naphthenes

21

and aromatics in multi ring structure along with sulphur, oxygen and nitrogen

compounds. It is black semi-solid materials with average number of molecular

weight around 11,800 g/mol. It is polar and sometimes can be more polar than

asphaltenes and functions as a stabilizer for the asphaltenes (Lesueur, 2009). Polar

aromatics are brown-black, adhesive, shiny solids or semi-solid which comprised

heterogeneous polar aromatics compounds with a small amount of oxygen, nitrogen

and sulphur with molecular weights of 800-2,000 g/mol and constitutes to 15-25% of

the total weight of bitumen (Hardee, 2005).

2.2.3 Bitumen chemical properties according to other methods

Separation and other characterization methods in analysing chemical properties of

bitumen may also be performed using other methods such as:

(i) Thin layer chromatography (TLC-FID),

(ii) Size exclusion (High Performance Gel Permeation Chromatography/HP-

GPC),

(iii) Ion Exchange Chromatography (IEC),

(iv) Characterization of Bitumen Chemical Properties According to Fourier

transforms infrared (FTIR) spectroscopy.

Comparing with Rostler and Corbett methods, these methods are faster and

more accurate however; the methods were not designed to extract the chemical

components of bitumen.

Even though Rostler and Corbett methods are classical, the two methods are

able to isolate and extract the chemical components. This feature enables the

investigation of the effect of individual chemical fraction on the characteristics of

bitumen.

2.2.3.1 Characterization of bitumen chemical properties based on thin-layer

chromatography with flame ionization detection (TLC-FID)

The TLC-FID is a method to analyse and separate bitumen into four fractions:

saturates, aromatics, resins, and asphaltenes. In the TLC-FID, 2% (w/v) solutions of

22

bitumen were prepared in dichloromethane, and 1 µl sample solution spotted on

Chromatography rods using a spotter. Bitumen is then separated into four generic

fractions (saturates, aromatics, resins and asphaltenes) by a three-stage development

using n-heptane, toluene and dichloromethane/methanol (95/5 by volume),

respectively. The fractions were determined by an Iatroscan MK-5 analyser (Lu &

Isacsson, 2002; Guern et. al., 2010).

TLC-FID test are faster and more accurate than the conventional tests

(Corbett and Rostler tests) in determining a chemical fraction composition of

bitumen however; the procedure cannot be used to extract and recover the chemical

fractions hence the chemical fraction cannot be analysed individually in identifying

its effect on the bitumen rheological characteristics. A research on the effect of

chemical properties on rheological characteristics can only be done by correlating or

regressing chemical composition or its change with rheological characteristics.

Percentage ratio of each chemical fraction in bitumen has strong correlation with

percentage ratio of another chemical fraction. It causes one or more chemical

fraction to become excluded variables. If percentage of one chemical fraction

decreased or increased, then percentage of the other fractions will increased or

decreased accordingly. As a consequence, it is not clear which fraction will affect

the rheological characteristics of the bitumen.

Lu & Issacsson (2002) conducted a chemical characteristic study on bitumen

and compared test results from TCL-FID and rheology. According to their study,

ageing of bitumen decreases aromatics and increases the content of resins and

asphaltenes at the same time. The content of saturates changes slightly due to their

inert nature to oxygen. However, as a result of the chemical changes, the

mechanical properties of aged bitumen become more solid-like, as indicated by

increased complex modulus and decreased phase angle. They also found the

chemical and rheological changes generally inconsistent.

Montepara & Giulani (2001) evaluated the chemical properties of bitumen

using TLC-FID of fresh, short-term ageing process by RTFOT and after long-term

ageing by PAV. They concluded that saturates remain substantially unchanged in

bitumen during short-term and long-term ageing process. On the other hand, the

reactivity of aromatics and resins to air induced the formation of polar groups, and

increased their concentration in bitumen significantly.

23

The other study was reported by Guern et.al. (2010). They used TLC–FID

Iatroscan to determine the colloidal instability index or Gaestel index (Ic). The index

is a ratio of asphaltenes and saturates percentage to aromatics and resin percentage.

It is typically used to characterize the colloidal stability of bitumen. It was

compared to the agglomerate content value determined by HS-SEC. The result

showed a significant evolution in agglomerate content hence the concept of stability

provided by the colloidal index did not appear to be systemically correlated with

agglomerate content.

2.2.3.2 Characterization of bitumen chemical properties based on high

performance gel permeation chromatography (HP-GPC)

HP-GPC involves the separation of bituminous materials into their components

according to molecular size. Size exclusion chromatography (HP-GPC) separates

components of the bitumen based on the apparent size (hydrodynamic volume) of

molecules and molecular aggregations or associations in dilute solution. The

chromatogram describes the molecular size profile of bitumen. For the purpose of

HP-GPC determination, the bitumen sample is introduced into a solvent (typically

tetrahydrofuran or toluene) flowing at high pressure through a column packed with a

highly porous, solid material. The liquid transports the asphalt through and around

the porous packing material in the column and as a result smaller size molecules in

the asphalt can enter freely into all the pores of the column packing while larger

molecules can enter none of those pores (Yapp et al., 1991).

Molecules of intermediate size have access to varying amounts of available

pore volume thus the larger molecules move through the column faster than the

smaller ones. The Large Molecular Size portion of the bitumen leaves the column

first, followed by the medium-size and then the small size components. A detector

measures the amount of each component. The resultant chromatogram represents

the relative amount of material appearing at a given elution time (Yapp et al., 1991).

Furthermore, Yapp et al. (1991) investigated the relationship between HP-

GPC parameters and performance of bituminous concrete pavements however; the

relationships are inconsistent and likely to be confounded by test method, methods

24

of interpretation of the HP-GPC test data, and relationship to different types of

pavement distress (i.e., transverse cracking, fatigue cracking, rutting or tender

mixes).

Even though the molecule size generally can affect the bitumen consistency,

it could be fuzzy if the molecule polarity or molecule structure is different. Polarity

and molecule structure that cannot be detected by HP-GPC can also affect the

bitumen consistency as shown in Table 2.2. Since the relationships between HP-

GPC parameters and bituminous consistency were not consistent, as a consequence,

the relationships of the parameters on rutting of bituminous pavement become

inconsistent as well.

On the other hand, molecules size of bitumen fractions cannot indicate

bitumen elasticity, brittleness and ageing reactivity hence it cannot indicate cracking

performance of the bituminous pavement.

Table 2.2: Viscosity of bitumen fractions at same average molecular weight(Petersen, 1982)

Fraction Polarity Apparent molecularwt.

ViscosityPa.S

Saturates Less polar 500 10Aromatics 500 1,000Resins More polar 500 100,00

2.2.3.3 Characterization of bitumen chemical properties based on Ion Exchange

Chromatography (IEC)

Ion exchange chromatography (IEC) is a technique used to separate bitumen into

distinct chemical fractions based on chemical functionality without the need for

initial asphaltene precipitation. IEC accomplishes this fractionation by pumping

solution of bitumen, dissolved in selected solvents, into columns filled with activated

cation or anion resins. Bitumen components containing acidic functional group

absorbed on anion resins, from which they can be desorbed. Bitumen component

having basic functional groups are absorbed in cation resins. Component containing

191

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